DE2630257C3 - New organic phosphites and their use as stabilizers - Google Patents

Description

is, in which R 1 to R ₄ stand for identical or different r> radicals, which can be

a) Obis3H atoms,

b) a phenyl radical optionally substituted by alkyl groups having 1 to 9 carbon atoms or a Cycloalkyl radical with 5 to 12 carbon atoms, '"

c) a straight-chain or branched alkyl radical with ί to 60 carbon atoms,

where the radicals indicated under c) optionally also ether, thioether, carboxylic acid ester η

-CII ₁ CH ₁ O

CH., - CH-CH ₂ O

O> -B

O> -B

in the

B = -O-, -S-, -CO-, -SO ₂ - or -><>

denotes, where D and E can be identical or different, Η atoms or alkyl radicals with 1 to 6 carbon atoms or common members of an alkylene chain with 4 up to 6 carbon atoms and the sum of all contained in the radicals R and R ' C atoms is at least 12, but not more than 120.

2. Phosphites according to claim 1, in which π = 1, R and R 'are identical or different and Ri is a straight-chain or branched alkyl group having 10 to 58 carbon atoms, R3 and R4 are hydrogen atoms, R2 is a hydrogen atom or a methyl - or can contain groups, and / or R2 and R _{3 can be} common members of an alkylene chain with 3 to 10 carbon atoms and the sum of all _{carbon atoms contained in Ri to R 4 is} at least 4, but not more than 60,

while any remaining radical R or R '

d) a phenyl radical optionally substituted by alkyl groups having 1 to 9 carbon atoms or a Cycloalkyl radical with 5 to 12 carbon atoms or

e) can be a straight-chain or branched alkyl radical with 1 to 60 carbon atoms,

where the radicals specified under e) can also optionally contain ether, thioether, carboxylic acid ester groups and the sum of all carbon atoms contained in the radicals R and R 'is at least 10, but not more than 120,
while η = 2 R and R 'are different, R' is the same or different in the two parts of the molecule connected by R and has the meaning given for η = 1 and R stands for a divalent organic radical that can be

f) one which is optionally substituted by methyl or ethyl groups and optionally by Ether, thioether or carboxylic acid ester groups interrupted ethylene chain with 2 to 16 Carbon atoms,

g) a phenylene radical optionally substituted by alkyl groups, one optionally substituted by 1 to 4 chlorine atoms substituted m- or p-xylylene radical, a 1,3- or 1,4-dimethylene tricyclodecane radical,

h) a group of the general formula

O> - B - <

OCH ₁ CH ₁ -

0-CH ₁ -CH-CH,

Is ethyl group and the sum of all carbon atoms in Ri to R ₄ IO to 60 is.

3. Use of phosphites according to claims 1 and 2 as stabilizers for organic Polymers in amounts of 0.01 to 10 parts by weight per 100 parts by weight of polymer, optionally in Combination with other known stabilizers, lubricants, plasticizers, pigments, Fillers and auxiliaries.

To minimize the damaging effects of heat and light on synthetic high polymers To limit, it is necessary to use stabilizers and stabilizing auxiliaries in the polymers to prevent them of decomposition phenomena to inflict. By adding stabilizers and Stabilizing auxiliaries can often achieve synergistic effects. Among the most common stabilizing auxiliaries include z. B. Epoxy compound

fertilize. Antioxidants, polyhydric alcohols, compounds that absorb ultraviolet rays, and organic phosphites.

Frequently, however, the stabilizing auxiliaries are not fully satisfactory and in some cases are even afflicted with several defects at the same time For example, a number of the known organic phosphites used for stabilization purposes have one insufficient resistance to hydrolysis and a relatively high volatility The demand for non-toxic properties is widely known by most Phosphates met only completely inadequately (DE-AS 1175 874; DE-PS 12 37 312; DE-OS 14 69 989 and 15 44 996; U.S. Patents 25 64 646, 29 61 454, 30 00 850; ). E. C a s i d a. Chem. Ing. News, 52 [1974], No. 1, p. 56).

It was therefore an object of the present invention to provide stabilizers based on organic phosphites find that do not have the disadvantages described and are stabilized by a high degree Distinguish effect.

Surprisingly, it has been found that the phosphites derived from pentaerythrityl diphosphite general formula

C) -CH ₂ CH ₂ -C)

RO - P C

P -O

C) -CH ₂ CH ₂ C)

211

with π = 1 or 2, where at

η = 1 R and R 'can be identical or different and at least one of these radicals is a group of the formula

K ₁ K, R ₁ -CC-

C) H

is, in which Ri to R4 are identical or different radicals stand, which can be

O> -B- <O

—CH, CH, C)

CH ₁ -CH-CH ₂ O

a) O to 3 H atoms,

b) a phenyl radical optionally substituted by alkyl groups having 1 to 9 carbon atoms or a Cycloalkyl radical with 5 to 12 carbon atoms or

"> c) a straight-chain or branched alkyl radical with 1 to 60 carbon atoms,

where the radicals indicated under c) optionally also ether, thioether or carboxylic acid ester groups

ίο can contain, and / or R ₂ and R, can be common members of an alkylene chain with 3 to 10 carbon atoms and the sum of all _{carbon atoms contained in Ri to R 4 is} at least 4, but not more than 60, during the optionally remaining radical R or

d) an optionally through alkyl groups with 1 to 9 Phenyl radical substituted by carbon atoms or a cycloalkyl radical having 5 to 12 carbon atoms or

e) can be a straight-chain or branched alkyl radical with 1 to 60 carbon atoms,

where the radicals given under e) can also optionally contain ether, thioether or carboxylic acid ester groups and the sum of all carbon atoms contained in the radicals R and R 'is at least 10, but not more than 120, while η = 2 R and R 'are different, R' in the two molecular particles connected by R is the same or different and has the meaning given for η = 1 and R here stands for a divalent organic radical which can be

f) an optionally substituted by methyl or ethyl groups and optionally by ether, Thioether or carboxylic acid ester groups interrupted ethylene chain with 2 to 16 carbon atoms,

g) a phenylene radical optionally substituted by alkyl groups, one optionally substituted by 1 to 4 Chlorine atoms substituted m- or p-xylylene radical, a 1,3- or 1,4-dimethylene cyclohexane radical Dimethylene iricyclodecane residue,

h) a group of the general formula

OCH ₂ CH ₂ -0-CH ₂ -CH-CH,

O V-B ^ C O '

B "<

in which B = -O-, -S-, -CO-, -SO ₂ - or DE

denotes, where D and E can be identical or different, Η atoms or alkyl radicals with 1 to 6 carbon atoms or common members of an alkylene chain with 4 to 6 C atoms can be and the sum of all C atoms contained in the radicals R and R 'at least 12, but not more than 120,

have the desired advantageous properties as far as possible.

The present invention accordingly relates to the previously unknown organic phosphites mentioned and their use as stabilizers for organic polymers.

A particular advantage of the phosphites according to the invention is their significantly greater insensitivity to hydrolytic influences compared to many phosphite stabilizers, which is reflected in a Improvement in the weathering resistance of the molding compositions stabilized with them expresses itself

Another advantage is that such Representatives of the new phosphites, which are in the form of substances that are solid at room temperature, with the their help processed plastic parts a higher

Lend heat resistance than can be achieved with the use of known liquid phosphites Finally, there is also a greatly reduced build-up of deposits on the processing machines as well observe a significantly reduced formation of grooves on the molded bodies produced. The odorlessness, the practically non-existent volatility and the lack of tendency to exudate are additional valuable properties.

Some of the phosphites according to the invention are still liquid at room temperature, but in general and preferably the new phosphites are solid white products with partly waxy character. The latter, which have pour point between about 35 and 100 ^° C., are of particular interest in addition to their stabilizing effect, they have a beneficial effect on the product properties of the polymeric molding compositions containing them.

The phosphites are by methods known per se by transesterifying tri-lower alkyl phosphites or triphenyl phosphite with pentaerythritol and further implementation of the primarily formed di-lower alkyl or diphenyl pentaerythrityldiphosphite with the Alcohols R-OH and / or R '- OH obtained.

In the phosphites of the general formula

Ο —CH ₂ CH ₂ -O

RO — P C Ρ — O

Ο —CH ₂ CH ₂ -O

Alkylene chain with 3 to 10, preferably 3 to 6 carbon atoms are. The new phosphites are further characterized in that the total number of all _{carbon atoms contained in the radicals R 1 to R 4} is now at least 4, preferably at least 8, but not more than 60

If R and R 'are different, then there are remaining R or R 'radical denotes a phenyl group, optionally substituted by 1 or 2 alkyl or isoalkyl groups having 1 to 9, preferably 1 to 4, carbon atoms can be substituted, for example a phenyl, tolyl, xylyl, tert-butylphenyl, nonylphenyl group, or can also represent a cycloalkyl radical having 5 to 12, preferably 5 to 7, carbon atoms. Finally and The radical R or R 'can preferably also have the meaning of a straight-chain or branched alkyl radical with 1 to 60, preferably 8 to 40 and in particular 10 to 30 carbon atoms. The remainder of R or R ' can optionally also contain ether, thioether or carboxylic acid ester groups. At different Residues R and R 'should be the sum of all carbon atoms contained in R and R' at least 10, but not more than 120.

If the index η in the general formula has the meaning of 2, then R and R 'are different radicals. R 'can be the same or different in the two parts of the molecule linked by the radical R and has the meaning given above for η = 1. Here R —R stands for a bivalent organic radical

At least one of the two radicals R 'stands for one Group of formula

is η = 1 or 2.

When π = 1, R and R 'stand for identical or different radicals, at least one of which is a group of the formula

R ₂

R ₁ -CC-

OH

is. Ri, R ₂ , Rj and R «are identical or different radicals, of which up to three can be hydrogen atoms. The remaining radicals either have the meaning of a phenyl group, which can optionally be substituted by 1 or 2 alkyl or isoalkyl groups with 1 to 9, preferably 1 to 4 carbon atoms, for example a phenyl, tolyl, xylyl, tert- Butylphenyl, nonylphenyl or can also represent a cycloalkyl radical with 5 to 12, preferably 5 to 7, carbon atoms. Finally and preferably, Rt to R * can also have the meaning of a straight-chain or branched alkyl radical having 1 to 60, preferably 8 to 40 and in particular 10 to 30 carbon atoms. The radicals Ri to R »can optionally also contain ether, thioether or carboxylic acid ester groups. It is also possible that the radicals R ₂ and R ₃ common members of a

CH ₂ CH ₂ O

* 2 Rl

R ₁ -CC-

R, OH

4 (i where Ri, R ₂ , R ₃ and R _{4 are} those for η = 1 and R = R ' have given meaning; the possibly the remainder of R 'then stands for one of those at η = 1 and R = Η R 'radicals.

The bivalent organic radical R means one of the

4 ') the following groups:

a) An alkylene chain with 2 to 16, preferably 2 to 12 carbon atoms, which is optionally substituted by methyl or ethyl groups and given

if it can be interrupted by ether, thioether or carboxylic acid ester groups. Examples are the ethylene, propylene, 2,2-dimethyl-propylene, butylene, pentylene, hexylene, 2-ethylhexylene, octylene, decylene or dodecylene group;

b) a phenylene radical optionally substituted by 1 or 2 alkyl groups having 1 to 9 carbon atoms m- or p-xylylene radical optionally substituted by 1 to 4 chlorine atoms, a 1,3- or 1,4-dimethylene cyclohexane residue or a di-

w) methylentricyclodecane radical;

c) a group of the general formula

OCH ₂ CH ₂ -

CII, -CM C II, O O C II, CH ΠΙ,

in the B the meaning of -Ο-, - S -, -CO -, C atoms contained at least 12, but not more

-SO ₂ - or as 120.

I)! Κι

\ / Typical representatives of the phosphate according to the invention

In the following, —C— te are arranged in five groups

enumerated, the invention is not intended to thereby

has, with D and E being the same or different, the substances mentioned are restricted. Descriptive

can, Η atoms or alkyl radicals with 1 to 6 i> Cn / n-alkyl, Cis / 22-alkyl, C22 / 2b-alkyl and

C-atoms mean or common Glicder Cjo-alky! state that the products are made by repositioning

an alkylene chain with 4 to 6 carbon atoms can be obtained from 1,2-alkanediol mixtures,
nen and the sum of all in the remainders R and R '

Group of phosphites in which / i = I and R = R 'or R =) ^: R', of the formula

O -CH, CH ₁ -O

R-CH-CH ₁ -OPC PO-CH ₁ -CH-R '

OH O-CH ₁ CH ₁ -O OH

R = R '= C, ₂ H25-n-alkyl - R '= Qo -alkyl R = R '= C, 2/14-alkyl R = R '= nC ₁₈ H ₃ 7 — S-CH ₂ - R '= Ci8 / 22-alkyl R = R '= C, « _{/ 2} 2-alkyi R = n-QH ₁₇ ; R '= Qa / aralkyl R = R '= C22 _{/ 2 (} , -alkyl R = C _{I2 / 14-} alkyI; R '= Cso -alkyl R = R '= Qfi -alkyl R = C _{12 / I4} -alkyl; R '= C ₂₂ / »- alkyl R = C ₁₂ ""alkyl; R '= QS -alkyl R = C _{I8 / 22} alkyl; R '= CSS -alkyl R = C _{I8 / 22} alkyl; R '= UC ₁₇ H ₃₅ -CO-O-CH ₂ R = Q 1-4 alkyl; R '= UC ₁₁ H ₃₅ - CO— Ο — CH ₂ R = _{C12 /} I4-alkyI; R '= Ti-C ₁₇ H ₃₅ -CO-O-CH ₂ R = C, _8/22 alkyl; Ti ' QH ₅ -O-CH ₂ - R = CiTi -alkyl; R = CiK -alkyl; R = R = nC, -, H ₃₅ —CO —Ο — CH ₂ - R = R = Q ₁ H ₅ -O-CH ₂

2. Group of phosphites in which η 1 and RI = R, of the formula

¹⁰

C) CII, CH, C)

R-CH CH, O P C P- O -R '

OH O CII, CH, -O

R - C _12; , 4-alk \ l: R ' = C _1K H., ₇ -ii-alkyl R = Cs, ₂ : alkyl; R ' = C _ls H ₁₇ -n-alkyl R - = Cv, -alkyl: R ' = C, «H, 7-n-alkyl R = C _1x ,,, - alkyl; R ' = Phenyl R = C.ii -alkyl: R ' = Phcnyl- R = Ci-alkyl; R ' = Nonylphenyl R = Culbrii-alkyl; R ' = Cyelohexyl- R = HC ₁₇ H ₁₅ CO —O — CH ₂ -; R ' = Phenyl R- = HC ₁₂ H ₂₅ -C) -CH ₂ -; R ' = C ₁₂ H ₂₅ n -alkyl R = CkH ₁₇ -O- (CH ₂ ), _{-0- (CH 2} I ₂ -O-CH ₂ -; R ' = Ο ,, Η ,,, - n-alkyl R - CH ₁ (CH ₂ I ₇ -CH = CH (CH ₂ I ₇ -CO-O CH ₂ -; R ' = C ,,, H _u -na] kyl R = phenyl: R ' = C, «H, 7-n-alkyI

3. Groups of phosphites in which «= 2 and R 'are identical or different radicals, of the formula

R O CH, CH, - C) C) -CH, CH, C) R '",

HC -CH, O -PC PO -ROP C PO-CH ₁ CH

OH

C) -CH, CH ₂ C)

C) CH, CH, -O

R '= R; ,, = C _{,,,, 4-} alkyl R' = Ri ₁ , = CHu-n-alkyl R '= Ri ,, = Cm ,,, - alkyl R' = RJ ₁ , = C.5r -alkyl R '= RJ ₁ , = phenyl - K (J, - Π- ^ ΐ2Γΐ25 yj L- Γ12 " = Km = n-CnHis — S — LH, -

R '= C, _{2 / u} -alkyl; RJ ₁ , = C _{IH / 22} -alkyl R '= C 12 _/ , 4-alkyl; RJi, = CiT, -alkyl R '= C, ", 2, -alkyl; RJ _n = Qn -aicyl

R = -CH ₂ -CH ₂ - - (CH ₂ I ₂ -O- (CH ₂ ), - - (CH,) ,,

- CH, CH, O

'? \ -

OCH, CH ₂

B = C (CH ₃ J ₂ -CO- -SO, - [H.

R = -CH ₂ -CH ₂ -

Il 12

4th group of phosphines in which ii ■ - 2 and R 'stand for identical or different resle, of the formula

RCH-CH ₁ -OP

OH

O CH, ClI, O

O CH, ClI, - O

P-O-R-O-P

() —CH, CH, -O

/ \
O-CH, CII, -O

P OR '

R ' = R "= C _{l (} , H. _U -n-alkyl R ' = R "= C _{1 (i} ll., 7-n-alkyl R ' = dialkyl: R " = C, "II., ₇ -n-alkyl R ' = Cs ,,, - alkyl; R " = C, "H., 7-n-iilkyl R ' = CiT ₁ -alkyl; R " = C, «H, 7-n-alkyl R ' = nC | ₇ H, s-CO-O-Cl R " = C, "H ₁₇ -n-alkyl R ' = C, ",,, - alkyl; R " = Phenyl R ' = Cs, alkyl; R ' = Phenyl R ' = C ₁₇ H ₁₅ -CO-O CW ₂ R " = Nonylphenyl R ' = C 1, H ₂₅ n -alkyl; R " = CviH.i-n-alkyl

- (CH,), - Ο - (CH,), -

tO!,) "-

\ -OCH, CH.

B = C (CH.,), -CO-

-SO, - H

The phosphites according to the invention, together with other generally known stabilizers, can have stabilizing properties Excipients, antioxidants, UV stabilizing Compounds, optionally also in the presence of z. B. lubricants, plasticizers, pigments, Fillers and auxiliaries and the like are used. They are used in amounts of 0.01 to 10, preferably 0.05 to 2.0 and especially 0.1 to 1 part by weight based on 100 parts by weight of polymer.

When processing chlorine-containing polymers, for example chloropolyethylene, hard and soft polyvinyl chloride, Polyvinylidene chloride, polyvinyl chloroacetate and vinyl chloride-oleefin copolymers brings an addition of the new phosphites in the presence of metal compounds known as stabilizers, 2-substituted indoles, preferably 2-phenylindole, Epoxy stabilizers and, if necessary, polyhydric alcohols, a significant improvement in heat and light stability.

Metal compounds known as stabilizers are to be understood as meaning: Ca-, Ba-, Sr-, Zn-, Cd-, Mg-, Al- and Pb soaps of aliphatic carboxylic acids or oxycarboxylic acids with about 8 to 32, preferably 8 to 20 C atoms, salts of these metals with aromatic • τ. Carboxylic acids (benzoates, salicylates) and (alkyl) phenates these metals, also organotin compounds, such as. B. Dialkyltin thioglycolates and carboxylates, optionally also neutral and basic lead salts of inorganic acids, such as sulfuric acid and phosphorous Acid.

Known epoxy stabilizers are, for example, more highly epoxidized fatty acids such as epoxidized soybean oil. Tall oil or linseed oil, epoxidized butyl oleate and higher epoxyalkanes.

Polyhydric alcohols are z. B. pentaerythritol, trimethylolpropane, sorbitol or mannitol, ie preferably alcohols with 5 or 6 carbon atoms and 3 to 6 OH groups.
A stabilizer combination for processing

There is, for example, ω halogen-containing polymeric molding compounds from 0.01 to 10, preferably 0.1 to 2.0 parts by weight of a phosphite according to the invention, 0.1 to 10 parts by weight of metal compounds known as stabilizers, 0.1 to 10 parts by weight of one

b5 known epoxy stabilizer and 0 to 1 part by weight of a polyhydric alcohol.

The new phosphites are also excellent for stabilizing polymers or copolymers

halogen-free olefins suitable. The light and thermal stability of, for example, polypropylene is ensured by the addition of the phosphites according to the invention, in particular in a mixture with phenolic and / or sulfidic stabilizers, significantly improved.

Phenolic and sulfidic stabilizers are the generally known heat and light stabilizers used in plastics processing understood, such as

3,5-Diteriiybutyi-4-hydroxypheny! Prepiüi! - acid esters,

2,6-di-tert-butyl-p-cresol,

Alkylidene-bis-aikylphenoie,

Ester the

Bis- (4'-hydroxy-3'-tert-butyiphenyi) -butyric acid,

Thiodipropionsäui ester of Fatty alcohols as well

Dioctadecyl sulfide or disulfide. A synergistically effective stabilizer combination for polymers or copolymers of halogen-free olefins z. B. from 0.05 to 5, preferably 0.05 to 1.0 part by weight of a phosphite according to the invention, 0.5 to 3 parts by weight of a known phenolic Stabilizer and / or 0.1 to 3 parts by weight of a known sulfidic stabilizer.

In addition, the stabilizer combination can also contain special ultraviolet stabilizers in one Amount of 0.1 to 3 parts by weight can be added. Known UV absorbers are for example

Alkoxyhydroxybenzophenones, Hydroxyphenylbenzotriazoles, Salicylic acid phenol esters, Benzoic acid hydroxyphenol ester,

Benzylidenemalonic acid mononitrile ester and so-called "quenchers" such as

Nickel chelates, Hexamethylphosphoric acid triamide or Piperidine stabilizers.

With stabilizer combinations of the phosphites according to the invention and known stabilizers can not only improves the stability of polyolefins, chloropolyolefins and chlorine-containing vinyl polymers but also those of polyesters, polyamides, polyacrylonitrile, polycarbonates, polysiloxanes, and polyethers. Polyurethanes and others

The following examples are intended to further illustrate the invention and the advantages of the new phosphites point out.

example 1

After purging with nitrogen, a 1 liter four-necked flask equipped with a stirrer, internal thermometer, gas inlet and descending condenser is filled with 68 g (0.5 mole) dry pentaerythritol, 166 g (1.0 mole) freshly distilled triethyl phosphite and 0.2 g of triethylamine are charged

Over 20 to 30 minutes the flask contents are heated in a gentle stream of nitrogen with stirring at 125 to 130 ° C, wherein the bo elimination of ethanol at an internal temperature of about 120 ⁰ C used in the course of a further 2 to 3 hours, the temperature the reaction mixture gradually increased with continued stirring of 130 ⁰ C to a final temperature from 175 to 180 ° C During this time, 90.7 g of ethanol are distilled off.

482 g (~ 1

45

Mol) of a 1,2-alkanediol mixture with an average Carbon number of 32. In the case of the spontaneous transesterification reaction, the distillation continues for a further 3 hours at the same rate Product temperature from 175 to 180 ° C 45.5 g of ethanol.

The total amount of the split off ethanol is thus 136.2 g = 98% of theory.

The slightly cloudy, yellowish reaction product is allowed to settle for about 15 minutes and then the decanted clear melt from a small amount of a soil body. After the melt has cooled down 557 g = 96.5% of theory are obtained di- (2 hydroxy-CB-alkylJ-pentaerythrityl diphosphite in the form of a white wax with a pour point of 82 to 84.5 ° C (determined according to DGF M III 3 [57]). Phosphorus content 5.1%, molecular weight 1210. Theory for a compound of the empirical formula C69H138O8P2 5.4% P and Molecular weight 1156.

Example 2

According to the detailed in Example 1 Procedure first 68 g (0.5 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite are reacted in the presence of 0.2 g of triethylamine.

Then 241 g (- 0.5 mol) of a 1,2-alkanediol mixture with an average carbon number of 32 and 164 g (~ 0.5 mol) of one 1,2-alkanediol mixture with 20 to 24 carbon atoms added.

After the transesterification has ended, 482 g = 96.4% of theory of a white, waxy phosphite with a pour point of 69 to 81.5 ° C. Phosphorus content 6.1%, molecular weight 980. Theory: P 6.2%, MW 1002

Example 3

According to Example 1, 68 g (0.5 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite are added in the presence implemented by 0.2 g of triethylamine

Thereafter, 241 g (~ 0.5 mol) of a 1,2-alkanediol mixture with an average carbon number of 32 and 122 g (-0.5 mol) of a 1,2-alkanediol mixture with 14 to 16 carbon atoms added.

This gives 450 g = 98% of theory of a yellowish waxy phosphite fluidized-dropping point 78 to 8I ⁰ Q phosphorus content of 6.6%, molecular weight 942. Theory: 63% P, MG 918th

Example 4

That according to Example 1 from 68 g (0.5 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite in the presence of 0.2 g of triethylanün reaction product obtained is reacted with 328 g (-1 mol) of a 1,2-alkanediol mixture having 20 to 24 carbon atoms

413 g = 97.4% of theory of a pure white, waxy phosphite from the pouring point are obtained 63 to 64 ° C phosphorus content 7.0%, molecular weight 807. Theory: 73% P, MW 848.

Example 5

According to Example 1, 68 g (04 mol) of pentaerythritol are obtained and 166 g (1.0 MoT) of triethyl phosphite reacted in the presence of 0.2 g of triethylamine

Then 164 g (-4 moles) of one 1 ^ -alkanediol mixture with 20 to 24 carbon atoms and 122 g (~ 04 mol) of an alkanediol mixture with 14 to 16 carbon atoms added.

After the transesterification reaction has ended, 367 g = 96% of theory of a yellowish, soft waxy phosphite with a pour point of 49 to 51 ° C obtain. Phosphorus content 7.7%, molecular weight 780. Theory: 8.1% P, MW 764.

Example 6

That according to Example 1 from 68 g (03 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite in the presence of 0.2 g of triethylamine obtained reaction product is reacted with 244 g (~ 1 mol) of a 1,2-alkanediol mixture with 14 to 16 carbon atoms

330 g = 97% of theory of a yellowish, soft wax-like phosphite with a pour point of 46 to 48 ° C. is obtained. Phosphorus content 9.1%, molecular weight 652. Theory: 9.1% P, MW 680.

Example 7

According to Example 1, 68 g (0.5 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite are added in the presence implemented by 0.2 g of triethylamine

Then 164 g (~ 03 mol) of a 1,2-alkanediol mixture with 20 to 24 carbon atoms and 179 g (0.5 mol) glycerol monostearate added.

After the transesterification reaction has ended, 420 g = 95.6% of theory of a white, waxy Phosphite obtained with a pour point of 52.5 to 53.5 ° C. Phosphorus content: 6.8%, molecular weight 874. Theory: 7.1% P, MW 878.

Example 8

The according to Example 1 from 68 g (03 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite in the presence of 0.2 g of triethylamine obtained reaction product is with a mixture of 164 g (~ 0.5 mol) of one 1,2-alkanediol mixture with 20 to 24 carbon atoms and 135 g (0.5 mol) of stearyl alcohol reacted.

375 g = 95% of theory of a pure white, soft wax-like phosphite with a pour point of 45 to 47 ° C. is obtained. Phosphorus content 7.7%, molecular weight 740.The theory: 7.8% P, MW 790.

Example 9

According to Example 1, 68 g (0.5 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite are added The presence of 0.2 g of triethylamine reacted.

Thereafter, 241 g (~ 03 mol) of a 1,2-alkanediol mixture with an average carbon number of 32 and 135 g (0.5 mol) of stearyl alcohol are added.

After the transesterification reaction has ended, 456 g = 96.5% of theory of a white, waxy Phosphite obtained from the pour point of 77 to 80'C. Phosphorus content 6.2%, molecular weight 922. Theory: 6.6% P, MW 944.

Example 10

According to Example 1, 68 g (03 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite in the presence of 0.2 g of triethylamine reacted

168 g (1.0 mol) of 3-phenoxypropanediol-1,2 are then added.

260 g = 98% of theory of a colorless, viscous phosphite with a phosphorus content of 10.8% and a molecular weight of 540. Theory: 11.7% P, MW 528.

Example 11

According to Example 1, 68 g (0.5 mol · pentaerythritol and 166 g (1.0 mol) of triethyl phosphite be "> Presence of 0.2 g of triethylamine implemented

Then a mixture of 241 g (~ 0, f MoI) a 1,2-alkanediol mixture with an average carbon number of 32 and 153 g (0.25 mol) Äthyle.i glycol added.

After the transesterification reaction has ended, 331 g = 94% of the theory of a white, waxy phosphite with a pour point of 793 to 82 ° C. Phosphorus content 83%, molecular weight 1335. Theory 8.8% P, MW 1410.

Example 12 According to Example 1, 68 g (03 mol) of pentaerythrii

and 166 g (1.0 mol) of triethyl phosphite in the presence

implemented by 0.2 g of triethylamine 2 "Then a mixture of 241 g (~ 0.5

Mol) of a 1,2-alkanediol mixture with an average Carbon number of 32 and 36 g (0.25 mol) 1,4-dimethyl

olcyclohexane added.

After the esterification reaction has ended, 358 g r> = 96% of the theory of a white, waxy

Phosphite obtained with a pour point of 81.5 to 85 ° C. Phosphorus content 8.2%, molecular weight 1400. Theory:

8.3% P, MW 1492.

_{J ()} Example 13

According to Example 1, 68 g (0.5 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite are added The presence of 0.2 g of triethylamine reacted.

Then a mixture of 164 g (~ 0.5 r> mol) of a 1,2-alkanediol mixture with 20 to 24 Carbon atoms and 79 g (0.25 mol) of 2,2-dimethyl-4,4'-bis (0-hydroxyethoxyphenyl) methane were added.

When the transesterification reaction has ended, 325 g are obtained

= 96% of the theory of a white, soft wax-like one

Phosphite obtained with a pour point of 53.5 to 55 ° C. Phosphorus content 8.6%, molecular weight 1448. Theory:

9.10 / 0 P ₁ MG 1356.

Example 14

4-, According to Example 1, 68 g (0.5 mol) of pentaerythritol and 166 g (1.0 mol) of triethyl phosphite reacted in the presence of 0.2 g of triethylamine

A mixture of 107 g (0.5 mol) of tetradecyl alcohol and 94 g (0.25 mol) of 2,2-dimethyl-4,4'-bis-i / f.y-dihydroxypropoxyphenyl-methane is then added.

291 g = 98% of the theory of a yellowish, soft wax-like phosphite with a pour point of 47.5 to 51 ° C., phosphorus content 9.8%, are obtained, Molecular weight 1120. Theory: 10.4% P, MW 1188.

Example 15

The procedure for determining the hydrolysis resistance of the new phosphites compared to that of four commercial products is as follows:

5 g of phosphite are heated to the boil in 100 ml of distilled water; after a boiling time of 20 or 60 minutes, the reaction mixture is cooled and the phosphorous acid content of the aqueous solution is determined by titration with 0.1N aqueous sodium hydroxide solution. The degree of hydrolysis of the phosphite investigated is arbitrarily defined as the ratio 100x / y, where χ is the volume of 0.1 n NaOH actually consumed and y is the theoretical volume of this

909 618/389

Reagem'.es is calculated assuming a complete hydrolysis of the phosphite to phosphorous acid.

Degree of hydrolysis in% after a boiling time of

20 min. 60 min.

Phosphite

a) triphenyl phosphite ¹ ) 84 100

b) Tris (nonylphenyl) phosphite ') 57 92

c) Diphenyl isooctyiphosphite ¹ ) 55 77

d) distearyl pentaerythrityl 52 68 diphosphite ')

Phosphite according to example)

e) 1 6.5 12.4

f) 2 13.8 19.5

g) 3 46 58.7 h) 4 44 56.3 i) 5 54 60.6 j) 6 62.2 68.4 k) 7 44 54.2 I) 8 48.1 54.9 m) 9 22 , 8 34.8 η) 10 81.2 88.6 ο) 11 17.4 25.5 ρ) 12 16.2 27.8 q) 13 39.2 51.6 r) 14 51.7 59.3

Ί Commercial ice cream products for comparison.

Examples 16 to 51

These examples show the stabilizing effect of the phosphites according to the invention during processing of PVC. The dynamic heat stability (Examples 16 to 33) and the static heat stability (Examples 34 to 51) were measured. The specified parts are always parts by weight.

Dynamic wire stability

In each case IOCi parts of a bulk polyvinyl chloride from K. value 60 with 0.2 parts of 2-phenylindole, 3 parts epoxidized soybean oil, 0.25 parts of a complex calcium / zinc stabilizer consisting of 42

^r > wt .-% calcium stearate, 30 wt .-% zinc stearate, 22 wt .-% pentaerythritol and 6 wt .-% 2,6-di-t-butyl-4-methyl-phenol, 0.2 parts of a montanic acid ester ( SZ 18, VZ 154), 03 parts of stearyl stearate, 0.5 parts of glycerol monostearate and 0.5 parts of the phosphites intimately

ι »mixed

For determining the dynamic Wärmestabil'tät the mixtures heated to a 180 ⁰ C laboratory two-roll mill to be applied and at a number of revolutions of 20 rpm within a minute

ι · '> a fur rolled by this at intervals Samples are taken from 10 minutes and their colors are compared with those of an internal color scale. the individual attempts run until the roller skin turns a dark brown to black color

- '<> assumes

To determine the static heat stability, is, as described above, firstly produced from the mixtures, a roll coat and this for 10 minutes at 180 ⁰ C on the roll mill rolled from the

Afterwards, about 0.5 mm thick platelets with a diameter of 30 mm are punched out from the roller. The platelets are wrapped with an aluminum foil and heated at 180 ^° C. in a heating cabinet with air circulation at intervals of 10 minutes

ι »a tile is then taken and its Color compared to the color scale.

In the color scale used, the numerals mean

. 1 = clear as water

2 = slight yellow tinge

3 = strong yellow color

4 = deep, yellow-brown color

5 - dark brown to black

As can be seen from the tables below, the PVC stabilized with the organic phosphites according to the invention is that with known phosphites as well as phosphite-free mixtures stabilized both in the dynamic and in the static

r> Thermal stability clearly superior.

Ex.
No. Phosphite
according to
example Discoloration of the mill skin
If 20 '30'
on color number 1 2 a rolling time of
40 ' 50 ' 6ff 70- 80 ' 16 1 1 1-2 2 2 3 3-4 4th 5 17th 2 1 2 2 2-3 3 3-4 4-5 5 18th 3 1 1-2 2 2-3 3 3-4 5 19th 4th 1 2 2-3 2-3 3 3-4 5 20th 5 1-2 2-3 2-3 3 3-4 3-4 5 21 6th 2 2 2-3 3 3 3-4 4th 5 22nd 7th 1-2 2 2 3 3-4 4th 4-5 5 23 8th 1 ~ 2 1-2 2 2-3 3 3-4 4th 5 24 9 1 2-3 2-3 2-3 3 3-4 4th 5 25th IO 2 1-2 2 3 3-4 4th 5 26th 11th 1 1 2-3 3 3-4 4-5 5 27 12th 1 2 3 * »4
J — t Λ
H 5

u Phosphine
according to
example Phosphite
according to
example 19th 26 30 257 1-2 2 2incr Walzzcit of
40 ' 50 * 20th 2 2 3 3 3-4 4th 70 " 80 " Forlsct / un 13th I. 2-3 2-3 2-3 3 1-2 2 2-3 3 3 4th 5 Ex.
No. 14th 2 Discoloration of the rolled skin at ι
10 "2ff 30"
on color number 2 2-3 3 3 6C 2 2 2-3 3 3 4th 4th 5 28 15a) 3 1 2 3 5 3-4 2 2-3 3 3 3 4th 29 15c) 4th 2 2-3 3 5 3-4 2 2 2-3 3 3 3 30 (cf.) I5d) 5 1 2-3 3-4 3 3-4 3 3 3 3-4 3-4 4-5 5 31 (cf.) without 6th 1 5 2 2-3 2-3 3 3-4 3-4 32 (cf.) Static thermal stability 7th 2 4-5 2 2-3 2-3 3 4th 5 33 (cf.) Ex.
No. 8th 2 2 2 2-3 3 3-4 3-4 from
8 (X 100 ' 34 9 2-3 2-3 3 3-4 4th 5 5 35 10 Discoloration of the fur in the air circulation drying cabinet during a tempering period
ff 20 "3ff W 50" 60 '7ff
on color number 1-2 2 2-3 3 3 4th 5 36 Il I. 2 2 3 3 3-4 4th 4-5 5 37 12th I. 2 2-3 3 3 3 4th 4-5 5 38 13th 1 3 3 3 3-4 3-4 4-5 3-4 5 39 14th 1 1-2 2 2-3 3 5 5 40 15a) 1-2 2 2 2 3 3-4 5 5 41 15c) 2 2-3 2-3 3 3-4 3-4 4th 42 15d) 1-2 2 2-3 3 3-4 3-4 5 5 43 without 1-2 44 I. 5 45 2 5 46 I. 4-5 5 47 I. 5 48 (cf.) I. 49 (cf.) 2 50 (cf.) I. 5 51 (cf.) I. 2 I.

Examples 52-55

These examples show that the addition of phosphites according to the invention significantly improved to polypropylene whose ^r> o light stability and heat aging resistance

Powder mixes consisting of

100 parts by weight of un stabilized polypropylene

(is | 23 (rqca. 8), 0.15 part by weight of O ": tadecyl-3- (3 ', 5'-di-tert-

butyl-4'-hydroxyphenyl) -

propionate and 0.10 parts by weight of the according to Examples 1.2

and 9 phosphites produced

are injected on an injection molding machine to form test panels 60 60 χ 1 mm Test specimen punched out

The light resistance is measured with the Xenotest device, Type 150, from Original Hanau Quarzlampen GmbH with the filter combination b IR + 1 UV according to DIN 53 387 checked. The exposure time was measured in 55 (cf.) Hours (= standing time) after which the absolute Elongation at break has fallen to 10%

The heat aging resistance measured on injection molded specimens based on DIN 53 383 at an air temperature of 140 ^° C. is used, in addition to determining the service life, to assess the phosphites according to the invention.

The following table shows the good light and heat-stabilizing effect of the phosphites according to the invention in polypropylene.

Light stability and heat aging resistance

b0

example Phosphites Service life warmth No. according to in hours aging example resistance in days 52 1 975 57 53 2 810 48 54 9 945 55

without

22nd

Claims (1)

Patent claims: formula \ PO O I. Phosphites of general O O-CH, CH ₁ - / \ / RO-P C
\ / \ O-CH, CH ₁ with π = 1 or 2, where η = 1 R and R 'can be identical or different and at least one of these radicals is a group of the formula π R ₁ R, Γ Γ R ₁ -CC- I.
R4 OH